Faculty of Science and Engineering

Department of Chemical Engineering

CHEN3000 Process Plant Engineering

Semester 2 2016

Individual Assignment 1

“I declare that this report is solely my own work. All contributions made by others have been
duly acknowledged.”

No. Miri/Perth ID Student’s Name Signature

1. 700025811/19352570 Rafael Damar Arjanggi

Date of Report Submission: September 14, 2017

Name of Lecturer: Dr Jibrail Kansedo
Faculty of Science and Engineering
Department of Chemical Engineering

Marking Criteria

No. Criteria Marks

1. Process survey and comparison

2. Process selection and justification

3. Synthesis of information and references

4. BFD

5. PFD

6. Presentation of report

Total

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Table of Content & Page Number

1. Introduction……………………………………………………………………….…………… 5

2. Coal Gasification to Produce Synthesis Gas

2.1. Fixed-Bed Gasifier……………………………………………………………..…..…… 6-7
2.2. Fluidized Bed Gasifier……………………………………………………….…………... 7
2.3. Entrained Flow Gasifier…………………………………………………....…………..... 8
2.4. Gasifier Comparison, Selection, & Justification………………………………………... 8-9

3. Water-Gas Shift to Improve Synthesis Gas Quality

3.1. Shift Temperature & Catalyst Comparison, Selection, & Justification……………..…… 9

4. Conversion of Synthesis Gas to Methanol

4.1 ICI Lozenge Quench Converter……………………………………………………..…... 10
4.2 Lurgi Combined Reactor………………………………………………………………… 11
4.3 Toyo Multi-Stage Radial Flow Reactor……………………………………………… 11-12
4.4 Converter Comparison, Selection, & Justification………………………………………. 12

5. Methanol Purification
5.1. Distillation Column System Comparison, Selection, & Justification…………………… 13

6. Overall Process Description………………………………………………...……….…….. 13-16

References……………………………………………………………………………………. 17-18

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List of Figures

2.0. Types of Gasifiers…………………………………………………………………………… 6

2.1. Schematic of Fixed-Bed Gasifier.………………………………………………………...…. 7
2.2. Schematic of Fluidized-Bed Gasifier………………………………………………….…….. 7
2.3. Schematic of Entrained Flow Gasifier………………………………………………….…… 8
4.1. Schematic of ICI Lozenge Quench Converter………………………………………...……. 10
4.2. Schematic of Lurgi Combined Reactor…………………………………………………..…. 11
4.3. Schematic of Toyo Radial Flow Reactor……………………………………………....…… 12
6.0. Block Flow Diagram (BFD) of Methanol Production from Coal……………………….….. 15
Process Flow Diagram (PFD) of Methanol Production from Coal…………………….…… 16

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1. Introduction
For many years, methanol has been regarded as one of the most easily and widely
available chemical product, as well as possible energy source. Four main sections in methanol
production involve the generation of synthesis gas (syngas), improvement of syngas quality,
conversion of syngas into methanol, and purification of methanol. The production of methanol
is considerably convenient as the feedstock is syngas. Principally, so long as the material
contains carbon, it can be converted into syngas.

Syngas primarily contains of carbon monoxide and hydrogen gas (along with some
carbon dioxide). This particular set of gases earns its’ name due to its flexibility, serving as an
intermediate to synthesize various products. The discovery of syngas, as described by J. Ebert
(2007) is attributed to engineers tinkering with the deforming powers of heat and pressure.
With the aim to recover the energy within the chemical bonds of agricultural residues or any
other profusion of carbohydrate-consisting leftovers, engineers attempted to break these
linkages and capture the energy released in the process (Jessica Ebert, 2007).

Latest discoveries have presented a more renewable and eco-friendly option of biomass
for conversion to syngas. However, coal remains popular as it is still the more efficient and
cost-effective resource in the industrial scale. Essentially, this is because biomass requires pre-
treatment to take full advantage of the more advanced coal-based technologies (A. van der
Drift & H. Boerrigter, 2006).

This report aims to device a process of methanol production using coal as feedstock.
The construction will compare available technologies in each of the four main sections.
Through advantage-disadvantage analysis, every choice can be properly justified and the
overall process can be formed. Cost and efficiency of the plant are typically the ultimate
criteria for selection. Along with a written description, a block flow diagram (BFD) and
process flow diagram (PFD) is developed as well.

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2. Coal Gasification to Produce Synthesis Gas

Syngas generation and purification is a crucial part of the overall methanol production
process. Usually, it represents up to 70-80% of total investment when the raw material is coal
(Bozzano, G. & Manenti, F., 2015). Hydrocarbon can be converted into gaseous element by
applying heat under pressure with steam. For coal conversion to syngas, this purpose can be
achieved using a gasification system. Although there are other aspects that could be further
examined, gasifier is the centrepiece of this process. Thus, technology of the gasifier is the focus
on this section. There are three major gasifier types implemented in the industry: fixed- or
moving-bed, fluidized-bed, and entrained flow.

Figure 1: Types of gasifiers: (a) fixed-bed (dry ash), (b) fluidized-bed, and (c) entrained flow
(Herbden, D. & Stroud, H. J. F., 1945)

2.1 Fixed-Bed Gasifier

Despite using a counter current, the fuel within the bed is not actually fixed. Instead it
moves through the unit due to gravity, along with the exerted ash. Therefore, the name ‘fixed- or
moving-bed’ is given. In fixed-bed gasification, coal feed is initially dried and preheated in the
upper layer, releasing volatile hydrocarbons. In the combustion zone, steam entered is to react
with the treated feed and carbon dioxide to result in raw gas (H2 and CO). Moreover, residual
carbon reacts with oxygen, generating heat for the actual gasification step. At the bottom of the

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gasifier, ash cooling and air preheat occurs. The order between combustion and gasification may
be switched as displayed in Figure 2.

Figure 2: Schematic of Fixed-Bed Gasifier (Monazam, E. R. & Shadle, L. J., 1998)

2.2 Fluidized-Bed Gasifier

The reactor involves a suspension of coal, char, and ash in the centre part, which is where
the gasification and devolatilization will take place. The feed is a finer crushed coal that is either
run dry or agglomerated. Generally, whilst feeding into the reactor’s top end, coal is pressurized
with nitrogen. This is called a ‘lock hopper’ system. Injection of steam is done through the
bottom. After the upward flow of steam exchanges heat with the falling coal, raw gas leaves
through an off-take in the upper part of the reactor. Cyclone is also used to recirculate the fines.
Overall, this system was aimed to provide a more thorough mixing, uniform temperatures, and
overcome size limitations of the fixed-bed gasifier (Kneupper, C. and Saathoff, L, 2000).

Figure 3: Schematic of Fluidized-Bed Gasifier (Food & Agricultural Organization of the United
Nations, 1986)

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2.3 Entrained Flow Gasifier

In an entrained gasifier, coal is co-currently fed with oxygen in a dilute stream and
chambered in high temperatures within 1300 – 1475°C (Kneupper, C. and Saathoff, L, 2000) and
high pressure (300 psia). Residence time is only in matter of seconds. The resulting crude gas
would then exit depending on where the outlet is positioned. As displayed in Figure 4, a cooling
system is commonly installed to capture any excess heat within the reaction chamber. Given the
high temperature involved, this gasifier melts the coal ash into vitreous slag granulates.
Afterwards, raw gas and slag is discharged into a quench section below the vessel. The quenching
causes the gas to cool down up to 220°C (Siemens AG, 2008) and solidifies the molten slag,
which accumulates at the bottom. The feed used can be either wet (slurry) or dry coal. Compared
to the two other gasifiers, this uses system has the highest oxygen requirement. Ultimately, this
system aims to create a feed-versatile, rapid, and high conversion process through high operating
temperature and pressure, as well as a very turbulent flow.

Figure 4: Schematic of Entrained Flow Gasifier (NETL, 2012)

2.4 Gasifier Comparison, Selection, & Justification

Fixed-Bed is incapable of processing caking coals. Despite of its’ good heat transfer to the
carbon source, the methane and tar created tends to create fouling in the pipelines. This is because
of low operating temperature and oxygen consumption. Moreover, the counter-current operation
allows the tar to pass through, which is could be costly to the downstream units. Post production
cleaning and scrubbing requires a considerable amount of energy and money.

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On the other hand, Fluidized-Bed is prone to slagging that reduces the fluidization itself.
While it is well known to promote better mixing and uniform temperatures, it still has a drawback
on the high temperature of the fuel gas exiting the reactor. Fine particles can escape with raw
syngas and this would require extra energy to clean. Moreover, ash may reside along with
partially reacted carbon in the vessel., causing slags within the system.
In the case of Entrained Flow Reactors, it provides high feed flexibility compared to the other
two reactors, at the expense of higher temperature and oxygen requirement. It requires very little
residence time as the combustion process is rapid fast. Higher oxygen demand is due to its’ low
heat transfer. However, this means that methane and tar would not form or reside in exiting
syngas. Overall, despite being more expensive, entrained flow reactor is a more practical choice
with not much caution for maintenance, making it an ideal process for coal gasification. Thus,
Entrained Flow Gasifier is the opted route for this plant.

3. Water-Gas Shift to Improve Quality of Synthesis Gas

There are several gas clean-up and conditioning processing steps, namely: cooling, scrubbing,
compression, shift conversion, and acid gas removal. Despite the importance of all those steps, the
highlight of quality improvement lies in the water gas shift, as it enables the syngas to have an
appropriate H2/CO ratio for conversion to methanol. Therefore, this section will analyse the
technology options for water-gas shift reaction (CO + H2O ↔ H2 + CO2). Advances in reactor
design is not very significant in this matter. However, selection of operating temperature and
catalyst is essential to obtain the best quality.

3.1 Shift Temperature & Catalyst Comparison, Selection, & Justification

High temperature shift utilizes iron-chrome formula of catalysts. These types of catalyst allow
installation of lower volume catalysts. However, it rapidly oxidizes and cannot cannot withstand
the partial pressure of steam as easily. Low temperature shift uses alumina based catalyst with
copper and zinc added on. These types of catalyst allow excellent selectivity to give low methanol
by-product formation (Johnson Matthey, 2017). Isothermal/medium temperature shift is for
thermally stable conditions within the process. This would not be ideal as fluctuations of the
temperature along the plant is of high occurance. Lastly, sour shift is considerably the most
versatile of all as it is capable of withstanding sharp temperature rises and drops. Furthermore, it

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can also stand against impurity contamination in the raw gas. Therefore, considering the need for
versatility in this practice, sour shift is the most suitable technique for this plant design.

4. Conversion of Syngas into Methanol

Methanol synthesis is an exothermic reaction, thus requiring a reactor that presents
efficient temperature control and recovery. However, low temperature and high pressure enables
maximum conversion into methanol. Therefore, in designing reactor, trade-off needs to be solved
between the economical effort by temperature control, equilibrium requirement for high
conversion per pass, and catalyst containment. In the industry, Existing reactor technologies that
are applied in the industry are gas phase reactors, most prominently the adiabatic reactor. Despite
the developments in liquid phase reactors, feasibility is still limited due to modelling and scale-up
issues (Bozzano, G. & Manenti, F., 2015). In this section, three of the most common industrial
reactors are evaluated, namely ICI Lozenge quench converter, Lurgi combined converter, and
Toyo multi-stage radial flow reactor (MRF).

4.1 ICI Lozenge Quench Converter

Johnson Matthey (formerly ICI) quench converter accounts for 60% of worldwide methanol
production (Tungler, A., 2016). This unit operates at low pressure (50-100 bar) and intermediate
temperature (approx. 270°C). The term ‘lozenges’ is the name of distributors used as medium for
of cooling gas insertion. These lozenges move horizontally across the converter. The
configuration involves multiple adiabatic beds in series within a single pressurized shell. Catalyst
of Cu/ZnO/Al2O3 is loaded only in one of the beds. This simple system can produce up to 3000
tons/day (Bozzano, G. & Manenti, F., 2015).

Figure 5: Schematic of ICI Lozenge Quench Converter (GBH Enterprises Ltd., 2013)
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4.2 Lurgi Combined Reactor

Lurgi quasi-isothermal reactors accounts for 30% of worldwide methanol production
(Tungler, A., 2016). The reactor design is a vertical shell and tube heat exchanger with fixed tube
sheets. It is widely utilized particularly in large-scale plants due to its ability to operate at high
space velocities, thus enabling high production capacities. The two-stage converter combines in
series isothermal reactor with a gas-cooled reactor. Firstly, the isothermal/water-cooled reactor
executes a partial conversion. This reactor operates at higher velocity and temperature than a
single-stage converter. To achieve this, the reactor needs to be made smaller to compensate and
allow high-pressure steam production, which controls the reaction temperature. In the second
reactor, cold feed gas (for first reactor) is pushed through tubes counter-currently with the reacting
gas (from first reactor). This causes a decrease of temperature along the reaction path. Moreover,
the equilibrium is preserved at a driving force over the catalyst bed.

Figure 6: Schematic of Lurgi Combined Reactor (Lurgi-Air Liquide, 2015)

4.3 Toyo Multi-Stage Radial Flow Reactor

The Toyo Engineering Corporation (TEC) reactor, is a multi-stage radial flow reactor (MFR) with
intermediate cooling. Operating temperature of this reactor is kept close to its maximum tolerable
value, allowing an optimal conversion per pass. Catalyst is inserted through concentric beds. The
mild temperature conditions allow an increased catalyst life. Volume of catalyst bed is also
reduced to about 30% of quench converters’. Heat removal and recovery is also conducted
efficiently via blade boiler tubes, which in turn can be used to synthesize syngas. The production
capacity is up to 5000-6000 tons/day (Bozzano, G. & Manenti, F., 2015).

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Figure 7: Schematic of Toyo Radial Flow Reactor (Toyo Engineering, 2015)

4.4 Converter Comparison, Selection, & Justification

Johnson Matthey (formerly ICI) low pressure quench converter is the most common
solution applied in industry. Simply put, it is a single bed divided into three parts by quench
addition (GBH Enterprises Ltd., 2013). The concept is simple but suffers high pressure drop and
could be costly if not under proper control. That is why the proposed utilization of the ICI unit is
to use two reactors to avoid the drastic pressure drop. However, the utilization of multiple reactors
also mean additional operating cost.
Lurgi is also widely used in the industry. Its’ layout ensures tight control of the
remperature profile and allows production of high-pressure steam (Bozzano, G. & Manenti, F.,
2015). It is recommended for producers to conduct a two-stage converter system like ICI.
However, the aim in here is to simply guarantee high production capacities efficiently. As Figure
6 reveals, the high-pressure steam from the first converter is brought to the second one counter-
currently with cold gas. This allows heat recovery, cost reduction, and the reaction driving force is
ultimately preserved. In a nutshell, Toyo MRF uses a steam raising mechanism with an axial-
radial concept. It has quite a simple mechanical design with inter-cooling and split converters with
heat recovery.
In selecting a design, the most fundamental principle is to avoid high pressured drop with
a high conversion per pass, which can be achieved via heat recovery. From the gathered profile of
all three reactors design, Lurgi provides the most sensible option with little risk. Thus, this plant
would conduct the Lurgi system for syngas to methanol conversion.

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5. Methanol Purification
Further treatment of methanol is based on distillation technology. The arrangement for
number of columns is dependent on the grade of methanol demanded. For fuel grade methanol,
use of single column (only topping column) should suffice. However, to fulfil AA grade (approx.
99.5% purity) and IMPCA specifications, multiple columns are required, usually two or three
would be used (Johnson Matthey, 2017). The multiple column would include a topping column
and one or two refining columns. A topping column is designated to remove low boiling
impurities (light ends). Through a direct sequence, the light ends (dimethyl ether, methyl formate,
acetone, dissolved gases) are removed from the distillate. A refining column is used through to
separate refined methanol from the heavy ends. Via a direct sequence, the desired methanol
product is released through the distillate, whilst fusel oil (ethanol, propanol, butanol) and water
are released in the bottoms. When using a two-column system, the fusel oil can either be removed
along with the water, or a bottom side stream could be introduced. The latter could be more
economical as it can result in a valuable by-product in fusel oil, without adding another expensive
column. However, this fusel oil would have a considerable amount of water still intact. Adding
another refining column for a three-column system could serve several purposes. It can be used to
further separate fusel oil from water for a purer by-product, or it can be used to break down the
components within the fusel oil itself for a more specific by-product component.

5.1 Distillation Column System Comparison, Selection, & Justification

Assuming the desired methanol product is AA grade, single column option should be
eliminated as it will not comply to standards. Two-column systems are the most typically utilized
route. In the case of high energy cost or the heat for distillation is not readily available, three
column systems are appropriate as they consume least heat (Johnson Matthey, 2017). However, it
should also be considered that distillation column is an expensive technology. Moreover, the
profit gained from the by-product is relatively low and focusing intensively on its’ treatment
would not be economical. Thus, assuming the cost of energy meets economical requirement, a
two-column system is the best option for this plant.

6. Overall Process Description

First, coal must go through preparation to ensure optimal condition for gasification
reaction. For this plant, it is decided that a 50-50 weight-percent coal-water slurry would befed to

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the gasifier. Despite the entrained flow gasifier’s capability to receive any type of coal, it has been
calculated by W. C Morel (1977) that at the same efficiency, slurry feeding system is more
economical than the lock hopper system. Moreover, the combination of slurry and entrained flow
gasifier is used by Texaco, a highly reputable utilizer of coal. After passing through the crusher
and wet milling machine (WMR), the slurry is conveyed straight to the gasifier without prior
drying. This is done to save cost as entrained flow gasifier is already operated at high temperature,
pressure, as well as having high oxygen requirement.
After the combustion and water quenching (to recover slag) inside the gasifier, raw syngas
leaves the vessel and undergoes cooling before entering the water scrubber. The post-gasification
slag is separated to obtain fine slag, which is put into a clarifier along with char residue from
scrubbing. The fine slag and char obtained can either be disposed or put on a recycle stream to be
milled again. Water separated from the clarifier is recycled back for scrubbing again. Afterwards,
syngas still must undergo sour shift and acid gas removal before being converted into methanol.
Sour shift is done to adjust the syngas to its’ most optimum condition for methanol conversion.
The most appropriate H2/CO ratio to produce methanol is 2:1. Acid Gas Removal (AGR) is done
in two steps. The first column functions as the H2S absorber to result in sweet gas. The second
column functions as the CO2 absorber, thus completing the syngas purification stage.
Furthermore, pure syngas is stored in a holding tank prior to conversion. In the conversion stage,
the syngas is pumped into a reactor which results in raw methanol. The product of the reaction is
still comprised of 20% water and other impurities.
For the methanol purification stage, it has been decided for a two-column distillation
system to be conducted. So, one topping column and one refining column is utilized for this
process. First, the topping column would remove vent gases in the distillate. The bottoms stream
would still comprise of around 79% methanol, 20% water, and some fusel oil (mostly ethanol).
After entering the refining column, pure (99.9%) methanol would be the top product, which is
valuable and desired from the purpose of this design. It is also decided that a side-exit stream is to
exert the fusel oil, which can be valuable for fuel related processes. Water would be the bottom
product with methanol still comprised in it, typically at below 10 ppm. In this condition, the water
can be re-utilized for some parts of the process. Therefore, it is wise to recycle the purge water
into the storage tank to be redistributed to other processes. Filtration might be required over time
to improve upon the water quality.

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Figure 8: Block Flow Diagram (BFD) of Methanol Production from Coal

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Figure 9: Process Flow Diagram (PFD) of Methanol Production from Coal

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References

Zheng, L. & E. Furinsky. 2004. “Comparison of Shell, Texaco, BGL and KRW gasifiers as part of
IGCC plant computer simulations.” Energy Conversion and Management 46 (1): 1767-1779.
doi:10.1016/j.enconman.2004.09.004.

W. C. Morel. 1977. “Economic Comparison of Coal Feeding Systems in Coal Gasification—Lock

Hopper vs Slurry.” ACS Div. Fuel Chem. Preprints 22 (7): 155-164.
web.anl.gov/PCS/acsfuel/preprint%20archive/Files/22_7_CHICAGO_08-77_0155.pdf

Kneupper, C. and Saathoff, L. 2000. Coal Gasification. Kirk-Othmer Encyclopedia of Chemical

Technology. 4th ed. New Jersey: Wiley.

Bozzano G. & F. Manenti. “Efficient Methanol Synthesis: Perspectives, Technologies and

Optimization Strategies.” Process in Energy and Combustion Science 56 (2016): 71-205.
doi:10.1016/j.pecs.2016.06.001

J. B. Hansen. 2015. “Methanol Production Technology: Todays and Future Renewable Solutions.”
Powerpoint presentation presented at Methanol Workshop, Lund University, March 17.
http://www.lth.se/fileadmin/mot2030/filer/9._Bogild_Hansen_-
_Methanol_Production_Technology_Todays_and_Future.pdf

D. H. Eastland. 1975. “Methanol from Coal.” ACS Div. Fuel Chem. Preprints 22 (6): 191-212.
https://web.anl.gov/PCS/acsfuel/preprint%20archive/Files/20_3_CHICAGO_08-75_0191.pdf

Salalah Methanol Company, L.L.C. 2017. Methanol Manufacturing Process. Accessed September
15, 2017.
http://www.smc.co.om/SitePages/Methanol.aspx

Johnson Matthey. 2017. Water Gas Shift Cataysts. Accessed September 15, 2017.
http://www.jmprotech.com/water-gas-shift-catalysts-katalco-johnson-matthey

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Johnson Matthey. 2017. Methanol Distillation Technology. Accessed September 15, 2017.
http://www.jmprotech.com/methanol-distillation-technology-johnson-matthey

G. B. Hawkins. 2013. Methanol Plant Theory of Distillation. Accessed September 15, 2017.
https://www.slideshare.net/GerardBHawkins/methanol-plant-theory-of-distillation

National Energy Technology Laboratory. 2017. Entrained Flow Gasifiers. Accessed September 15,
2017
https://www.netl.doe.gov/research/coal/energy-systems/gasification/gasifipedia/entrainedflow

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